CN105185987B - Positive electrode and lithium rechargeable battery - Google Patents

Positive electrode and lithium rechargeable battery Download PDF

Info

Publication number
CN105185987B
CN105185987B CN201410233927.XA CN201410233927A CN105185987B CN 105185987 B CN105185987 B CN 105185987B CN 201410233927 A CN201410233927 A CN 201410233927A CN 105185987 B CN105185987 B CN 105185987B
Authority
CN
China
Prior art keywords
positive electrode
polycrystalline particle
lithium
life
licoo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410233927.XA
Other languages
Chinese (zh)
Other versions
CN105185987A (en
Inventor
种晋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningde Amperex Technology Ltd
Original Assignee
Ningde Amperex Technology Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningde Amperex Technology Ltd filed Critical Ningde Amperex Technology Ltd
Priority to CN201410233927.XA priority Critical patent/CN105185987B/en
Priority to US14/723,273 priority patent/US20150349330A1/en
Publication of CN105185987A publication Critical patent/CN105185987A/en
Application granted granted Critical
Publication of CN105185987B publication Critical patent/CN105185987B/en
Priority to US16/115,395 priority patent/US20180366720A1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a kind of positive electrode and lithium rechargeable battery.The positive electrode includes cobalt acid lithium LiCoO2And iron manganese phosphate for lithium LiFe (LCO)xMn1‑xPO4(LFMP), wherein, 0<x≤0.4；The iron manganese phosphate for lithium LiFexMn1‑xPO4With the cobalt acid lithium LiCoO2Mass ratio be m, and 0<m≤0.45；The iron manganese phosphate for lithium LiFexMn1‑xPO4For the polycrystalline particle with olivine structural；The cobalt acid lithium LiCoO2For the polycrystalline particle with layer structure；The iron manganese phosphate for lithium LiFexMn1‑xPO4Polycrystalline particle average grain diameter D50 be less than the cobalt acid lithium LiCoO2Polycrystalline particle average grain diameter D50, and the iron manganese phosphate for lithium LiFexMn1‑ xPO4Polycrystalline particle be filled in the cobalt acid lithium LiCoO2Polycrystalline particle between.The lithium rechargeable battery includes aforementioned positive electrode material.Lithium rechargeable battery of the present invention has high voltage platform and high energy density, while having good high rate performance, cycle performance and security performance.

Description

Positive electrode and lithium rechargeable battery
Technical field
The present invention relates to cell art, more particularly to a kind of positive electrode and lithium rechargeable battery.
Background technology
With traffic, communication and information industry develop rapidly and energy crisis increasingly serious, electric car and each Plant portable set and active demand is proposed to high performance alternative energy.Lithium rechargeable battery is used as a kind of chemical-electrical Source, because turning into the ideal chose of alternative energy with energy density height, good cycle and the low advantage of self-discharge rate. Lithium rechargeable battery is while possessing many advantages, and energy density, security, production cost and cycle life turn into system About its development key factor.And the positive electrode of above-mentioned factor and lithium rechargeable battery and negative material is physical Matter, chemical property, electrochemical properties and its compatibility with electrolyte are closely related.Wherein, positive electrode is to lithium ion two The influence of the performance of primary cell is especially pronounced.Therefore, exploitation is with high power capacity, low cost, security be good, compatible strong positive pole Material, as one of key of performance for improving lithium rechargeable battery.
At present, the positive electrode of conventional lithium rechargeable battery mainly includes three kinds：LiM with spinel structure2O4 (M=Co, Ni, Mn etc.), layer structure lithium-containing transition metal oxide LiMO2(M=Mn, Co, Ni etc.) and olivine knot The phosphoric acid lithium salts LiMPO of structure4(M=Fe, Mn, Co, Ni etc.).The LiM of spinel structure2O4Typical Representative be LiMn2O4, LiMn2O4Synthesize simple, cheap, high rate performance and have a safety feature, but due to electric discharge latter stage Mn3+The hair of disproportionation The high oxidative Mn that the raw, aggravation of John-Teller effects and latter stage of charging occur4+The decomposition of electrolyte can be triggered, and then The capacity of lithium rechargeable battery is caused to be decayed rapidly, the particularly decay during high temperature circulation is more notable.In addition, LiMn2O4Actual gram volume it is relatively low, further limit the application of lithium rechargeable battery.The gold of transition containing lithium of layer structure Belong to oxide LiMO2Typical Representative be LiCoO2(LCO), LCO synthesis is simple, technology maturation, gram volume are high, energy density is big, Good rate capability, is most long, widest in area positive electrode of current commercial applications time, but the Co elements price in LCO it is high, Toxicity is big, and the heat endurances of LCO in itself are relatively low, security performance is poor, therefore LCO is mainly used in the secondary electricity of small lithium ion Chi Zhong, and in large-scale lithium rechargeable battery, especially in terms of the electrokinetic cell of high-energy-density and high power capacity is needed Using being greatly limited.The phosphoric acid lithium salts LiMPO of olivine structural4Typical Representative be LiFePO4, LiFePO4Have Higher available gram volume, security, heat endurance, preferable cycle performance and relatively low cost, and it is environmentally safe, Make it that there is huge application prospect in terms of large-scale lithium rechargeable battery.But LiFePO4Electrical conductivity, tap density with And compacted density is relatively low, be unfavorable for obtain high-energy-density lithium rechargeable battery, thus limit its small-sized lithium from Application in terms of sub- secondary cell and electrokinetic cell.
LiFexMn1-xPO4(LFMP) as a kind of emerging olivine structural material, LiFePO is had concurrently4And LiMnPO4's Advantage, with higher energy density, higher security performance and preferable cycle performance.Simultaneously LFMP it is with low cost, with The compatibility of electrolyte is good, with higher available gram volume (>150mAh/g) and higher working voltage platform.In addition, Modified by carbon coating etc., LFMP can also obtain preferable high rate performance.But LFMP tap density and compacted density compared with It is low, cause its energy density relatively low.
In addition, the particle size of particle can also influence the performance of lithium rechargeable battery.The smaller LCO of particle diameter is in identical electricity The de- lithium of pressure is more, causes that its structural stability is poor, electrolyte consumption increase.And the larger LCO decapacitation of particle diameter is obtained Outside higher structural stability and heat endurance, also help and realize larger compacted density, so that it is close to obtain higher energy Degree and bigger available gram volume, but the ability that lithium rechargeable battery adsorbs electrolyte can be reduced, cause lithium ion secondary The generation for liquid behavior that battery is swollen.
The content of the invention
In view of problem present in background technology, present invention aims at provide a kind of positive electrode and lithium ion secondary electricity Pond, the lithium rechargeable battery has high voltage platform and high energy density, at the same have good high rate performance, Cycle performance and security performance.
To achieve these goals, in the first aspect of the present invention, the invention provides a kind of positive electrode, it includes cobalt Sour lithium LiCoO2And iron manganese phosphate for lithium LiFe (LCO)xMn1-xPO4(LFMP), wherein, 0<x≤0.4；The iron manganese phosphate for lithium LiFexMn1-xPO4With the cobalt acid lithium LiCoO2Mass ratio be m, and 0<m≤0.45；The iron manganese phosphate for lithium LiFexMn1- xPO4For the polycrystalline particle with olivine structural；The cobalt acid lithium LiCoO2For the polycrystalline particle with layer structure；The phosphorus Sour ferromanganese lithium LiFexMn1-xPO4Polycrystalline particle average grain diameter D50 be less than the cobalt acid lithium LiCoO2Polycrystalline particle it is flat Equal particle diameter D50, and the iron manganese phosphate for lithium LiFexMn1-xPO4Polycrystalline particle be filled in the cobalt acid lithium LiCoO2Polycrystalline Between grain.
In the second aspect of the present invention, the invention provides a kind of lithium rechargeable battery, it includes：Negative plate, including Negative current collector, it is arranged on negative current collector and the cathode membrane comprising negative material；Positive plate, including plus plate current-collecting body, It is arranged at the positive pole diaphragm on plus plate current-collecting body and comprising positive electrode；Barrier film, is interval between negative plate and positive plate；With And electrolyte.Wherein, the positive electrode is the positive electrode according to first aspect present invention.
Beneficial effects of the present invention are as follows：
1. the LiFe of the present inventionxMn1-xPO4Polycrystalline particle have higher porosity and specific surface area, have with electrolyte Stronger compatibility, is filled with LiCoO larger average grain diameter D502Polycrystalline particle between, positive pole material can be effectively improved The electrolyte adsorbance of material, while high rate performance, the cycle performance of lithium rechargeable battery is improved, and does not produce liquid change of rising Shape etc. is damaged, so as to improve the security performance of lithium rechargeable battery.
2. the LiCoO of the present invention2Average grain diameter D50 it is larger, higher structural stability and heat endurance can be obtained, had Beneficial to larger compacted density is realized, so as to improve the energy density of positive electrode.In addition, LiFexMn1-xPO4For LiCoO2 The expansion produced during Li insertion extraction/contraction provides certain cushion space, can also make up LiFexMn1-xPO4In compacted density The deficiency of aspect, reduces its influence to maximum system energy density, so as to improve Stability Analysis of Structures of the positive electrode in cyclic process Property.
3. the LiFe of the present inventionxMn1-xPO4With higher heat endurance and chemical stability, it can effectively reduce and store Electrolyte is alleviated in the generation rate of the side reactions such as the oxidation Decomposition of pole piece and BES is in cyclic process in journey Consumption, so as to improve the storage performance of lithium rechargeable battery, and greatly improve the security performance of lithium rechargeable battery.
4. the LiFe of the present inventionxMn1-xPO4It is with low cost, it can effectively reduce the cost of the raw material of lithium rechargeable battery Expenditure, it is easy to accomplish industrialization.
Embodiment
The following detailed description of the positive electrode according to the present invention and lithium rechargeable battery and embodiment, comparative example and survey Test result.
Illustrate positive electrode according to a first aspect of the present invention first.
Positive electrode according to a first aspect of the present invention includes cobalt acid lithium LiCoO2And iron manganese phosphate for lithium (LCO) LiFexMn1-xPO4(LFMP), wherein, 0<x≤0.4；The iron manganese phosphate for lithium LiFexMn1-xPO4With the cobalt acid lithium LiCoO2's Mass ratio is m, and 0<m≤0.45；The iron manganese phosphate for lithium LiFexMn1-xPO4For the polycrystalline particle with olivine structural；Institute State cobalt acid lithium LiCoO2For the polycrystalline particle with layer structure；The iron manganese phosphate for lithium LiFexMn1-xPO4Polycrystalline particle Average grain diameter D50 is less than the cobalt acid lithium LiCoO2Polycrystalline particle average grain diameter D50, and the iron manganese phosphate for lithium LiFexMn1-xPO4Polycrystalline particle be filled in the cobalt acid lithium LiCoO2Polycrystalline particle between.
In positive electrode described according to a first aspect of the present invention, x preferably can be 0.25≤x≤0.4.Within this range It can guarantee that iron manganese phosphate for lithium LiFexMn1-xPO4With cobalt acid lithium LiCoO2With close voltage platform (3.7V), so as to ensure to make Power output with its lithium rechargeable battery is constant.If x>0.4, then iron manganese phosphate for lithium LiFexMn1-xPO4Voltage platform (3.2V) is far below cobalt acid lithium LiCoO2Voltage platform (3.7V).
In positive electrode described according to a first aspect of the present invention, the iron manganese phosphate for lithium LiFexMn1-xPO4Polycrystalline Particle can be secondary polycrystalline particle.
In positive electrode described according to a first aspect of the present invention, the iron manganese phosphate for lithium LiFexMn1-xPO4It is secondary Polycrystalline particle can be oblate spheroid, elliposoidal or spherical.
In positive electrode described according to a first aspect of the present invention, the iron manganese phosphate for lithium LiFexMn1-xPO4It is secondary Polycrystalline particle can have porous network structure.LiFexMn1-xPO4Porous network structure can make it have larger available gram and hold Amount and higher working voltage platform, and can be with LiCoO2Match, so as to ensure LiCoO2Advantage in energy density. In addition, can also pass through LiFexMn1-xPO4Higher discharge platform improve the discharge potential of positive electrode, reduce positive electrode The polarization impedance on surface, makes up LiFexMn1-xPO4Deficiency in energy density, makes lithium rechargeable battery have higher energy The cycle life of metric density and length.
In positive electrode described according to a first aspect of the present invention, the iron manganese phosphate for lithium LiFexMn1-xPO4It is secondary The average grain diameter D50 of polycrystalline particle can be 2.5 μm~15 μm.
In positive electrode described according to a first aspect of the present invention, the iron manganese phosphate for lithium LiFexMn1-xPO4It is secondary The average grain diameter D50 of polycrystalline particle can be 7 μm~8 μm.
In positive electrode described according to a first aspect of the present invention, the iron manganese phosphate for lithium LiFexMn1-xPO4It is secondary The specific surface area BET of polycrystalline particle can be 10m2/ g~30m2/g。
In positive electrode described according to a first aspect of the present invention, the iron manganese phosphate for lithium LiFexMn1-xPO4It is secondary The specific surface area BET of polycrystalline particle can be 20m2/g。
In positive electrode described according to a first aspect of the present invention, the cobalt acid lithium LiCoO2Polycrystalline particle be averaged Particle diameter D50 can be 5 μm~20 μm.
In positive electrode described according to a first aspect of the present invention, the cobalt acid lithium LiCoO2Polycrystalline particle be averaged Particle diameter D50 can be 9 μm~10 μm.
In positive electrode described according to a first aspect of the present invention, the cobalt acid lithium LiCoO2Polycrystalline particle ratio table Area B ET can be 0.1m2/ g~0.6m2/g。
In positive electrode described according to a first aspect of the present invention, the cobalt acid lithium LiCoO2Polycrystalline particle ratio table Area B ET can be 0.5m2/g。
In positive electrode described according to a first aspect of the present invention, the iron manganese phosphate for lithium LiFexMn1-xPO4Polycrystalline Particle is in the cobalt acid lithium LiCoO2Polycrystalline particle between distribution mode can be uniformly continuous distribution or uniform discontinuous point Cloth.
Secondly lithium rechargeable battery according to a second aspect of the present invention is illustrated.
Lithium rechargeable battery according to a second aspect of the present invention, including：Negative plate, including negative current collector, be arranged at On negative current collector and the cathode membrane comprising negative material；Positive plate, including plus plate current-collecting body, be arranged on plus plate current-collecting body And the positive pole diaphragm comprising positive electrode；Barrier film, is interval between negative plate and positive plate；And electrolyte.The positive pole Material is the positive electrode according to first aspect present invention.
In lithium rechargeable battery described according to a second aspect of the present invention, the negative material may be selected from graphite, silicon, One kind in Si oxide, graphite/silicon, graphite/Si oxide, graphite/silicon/Si oxide.
In lithium rechargeable battery described according to a second aspect of the present invention, the plus plate current-collecting body can be Al paper tinsels.
Next explanation is according to the positive electrode of the present invention and the embodiment and comparative example of lithium rechargeable battery.Its In, LiCoO2From Hunan Ruixiang New Material Co., Ltd, LiFexMn1-xPO4From the limited public affairs of the great first material science and technology in Hubei Department.
Embodiment 1
1. prepare the positive plate of lithium rechargeable battery
LiCoO will be included2And LiFe0.25Mn0.75PO4Positive electrode (wherein, LiFe0.25Mn0.75PO4And LiCoO2Matter Amount is than being 0.05；LiCoO2Polycrystalline particle average grain diameter D50 be 13 μm, specific surface area BET be 0.5m2/g； LiFe0.25Mn0.75PO4Polycrystalline particle be oblate spheroid secondary polycrystalline particle, the average grain diameter D50 of polycrystalline particle is 7.5 μm, Specific surface area BET is 20m2/g；LiFe0.25Mn0.75PO4Polycrystalline particle in LiCoO2Polycrystalline particle between uniformly continuous point Cloth), binding agent PVDF, conductive agent Super-P and solvent NMP in mass ratio 21.8:1.6:1.6:It 75.0 is mixed evenly, Anode sizing agent is made, then anode sizing agent is uniformly coated on positive and negative two surfaces of plus plate current-collecting body Al paper tinsels and dried, is obtained To positive pole diaphragm, afterwards by cold pressing, section, soldering polar ear, the positive plate of lithium rechargeable battery is obtained.
2. prepare the negative plate of lithium rechargeable battery
By negative material Delanium, binding agent SBR/CMC, conductive agent carbon black in mass ratio 92.5:6:1.5 are dissolved in solvent In deionized water, stir and cathode size is made, the negative current collector Cu paper tinsels for being then uniformly coated on cathode size are just On anti-two surfaces and dry, obtain cathode membrane, afterwards by cold pressing, section, soldering polar ear, obtain lithium rechargeable battery Negative plate.
3. prepare the electrolyte of lithium rechargeable battery
By LiPF6With non-aqueous organic solvent (ethylene carbonate:Diethyl carbonate:Methyl ethyl carbonate:Ethenylidene carbon Acid esters=8:85:5:2, mass ratio) with 8:The solution that 92 mass ratio is formulated as lithium rechargeable battery electrolyte.
4. prepare lithium rechargeable battery
After the positive plate of preparation, PE barrier films and negative plate are wound, naked battery core is obtained, then welded by terminal, Aluminium foil encapsulation, injection electrolyte, chemical conversion, pumping shaping obtain lithium rechargeable battery.
Embodiment 2
Method according to embodiment 1 prepares lithium rechargeable battery, is simply preparing the positive plate of lithium rechargeable battery The step of (i.e. step 1) in, LiFe0.25Mn0.75PO4And LiCoO2Mass ratio be 0.10, LiFe0.25Mn0.75PO4Average grain Footpath D50 is 10.0 μm, specific surface area BET is 15m2/g。
Embodiment 3
Method according to embodiment 1 prepares lithium rechargeable battery, is simply preparing the positive plate of lithium rechargeable battery The step of (i.e. step 1) in, LiFe0.25Mn0.75PO4And LiCoO2Mass ratio be 0.20；LiCoO2Polycrystalline particle be averaged Particle diameter D50 is 20 μm, specific surface area BET is 0.3m2/g；LiFe0.25Mn0.75PO4Average grain diameter D50 for 15.0 μm, compare surface Product BET is 10m2/g。
Embodiment 4
Method according to embodiment 1 prepares lithium rechargeable battery, is simply preparing the positive plate of lithium rechargeable battery The step of (i.e. step 1) in, LiFe0.25Mn0.75PO4And LiCoO2Mass ratio be 0.30.
Embodiment 5
Method according to embodiment 1 prepares lithium rechargeable battery, is simply preparing the positive plate of lithium rechargeable battery The step of (i.e. step 1) in, LiFe0.25Mn0.75PO4And LiCoO2Mass ratio be 0.45.
Embodiment 6
Method according to embodiment 1 prepares lithium rechargeable battery, is simply preparing the positive plate of lithium rechargeable battery The step of (i.e. step 1) in, positive electrode include LiCoO2And LiFe0.10Mn0.90PO4.Wherein, LiFe0.10Mn0.90PO4With LiCoO2Mass ratio be 0.30；LiFe0.10Mn0.90PO4Polycrystalline particle be oblate spheroid secondary polycrystalline particle.
Embodiment 7
Method according to embodiment 1 prepares lithium rechargeable battery, is simply preparing the positive plate of lithium rechargeable battery The step of (i.e. step 1) in, positive electrode include LiCoO2And LiFe0.20Mn0.80PO4.Wherein, LiFe0.20Mn0.80PO4With LiCoO2Mass ratio be 0.30；LiCoO2Polycrystalline particle average grain diameter D50 be 20 μm, specific surface area BET be 0.3m2/g； LiFe0.20Mn0.80PO4Polycrystalline particle be elliposoidal secondary polycrystalline particle；LiFe0.20Mn0.80PO4Polycrystalline particle exist LiCoO2Polycrystalline particle between it is uniform discontinuously arranged.
Embodiment 8
Method according to embodiment 1 prepares lithium rechargeable battery, is simply preparing the positive plate of lithium rechargeable battery The step of (i.e. step 1) in, positive electrode include LiCoO2And LiFe0.30Mn0.70PO4.Wherein, LiFe0.30Mn0.70PO4With LiCoO2Mass ratio be 0.30；LiFe0.30Mn0.70PO4Polycrystalline particle be elliposoidal secondary polycrystalline particle； LiFe0.30Mn0.70PO4Polycrystalline particle in LiCoO2Polycrystalline particle between it is uniform discontinuously arranged.
Embodiment 9
Method according to embodiment 1 prepares lithium rechargeable battery, is simply preparing the positive plate of lithium rechargeable battery The step of (i.e. step 1) in, positive electrode include LiCoO2And LiFe0.40Mn0.60PO4.Wherein, LiFe0.40Mn0.60PO4With LiCoO2Mass ratio be 0.30；LiCoO2Polycrystalline particle average grain diameter D50 be 15 μm, specific surface area BET be 0.4m2/g； LiFe0.40Mn0.60PO4Polycrystalline particle be elliposoidal secondary polycrystalline particle；LiFe0.40Mn0.60PO4Polycrystalline particle exist LiCoO2Polycrystalline particle between it is uniform discontinuously arranged.
Embodiment 10
Method according to embodiment 1 prepares lithium rechargeable battery, is simply preparing the positive plate of lithium rechargeable battery The step of (i.e. step 1) in, positive electrode include LiCoO2And LiFe0.30Mn0.70PO4.Wherein, LiFe0.30Mn0.70PO4With LiCoO2Mass ratio be 0.30；LiFe0.30Mn0.70PO4Polycrystalline particle for elliposoidal secondary polycrystalline particle and with porous Network structure, the average grain diameter D50 of polycrystalline particle is 7.5 μm, specific surface area BET is 25m2/g；LiFe0.30Mn0.70PO4It is many Brilliant particle is in LiCoO2Polycrystalline particle between it is uniform discontinuously arranged.
Comparative example 1
Method according to embodiment 1 prepares lithium rechargeable battery, is simply preparing the positive plate of lithium rechargeable battery The step of (i.e. step 1) in, positive electrode is LiCoO2, LiCoO2Polycrystalline particle average grain diameter D50 for 13 μm, compare surface Product BET is 0.5m2/g。
Comparative example 2
Method according to embodiment 1 prepares lithium rechargeable battery, is simply preparing the positive plate of lithium rechargeable battery The step of (i.e. step 1) in, positive electrode is LiFe0.25Mn0.75PO4, LiFe0.25Mn0.75PO4Polycrystalline particle average grain diameter D50 is 7.5 μm, specific surface area BET is 20m2/g。
Comparative example 3
Method according to embodiment 1 prepares lithium rechargeable battery, is simply preparing the positive plate of lithium rechargeable battery The step of (i.e. step 1) in, positive electrode include LiCoO2And LiFe0.50Mn0.50PO4.Wherein, LiFe0.50Mn0.50PO4With LiCoO2Mass ratio be 0.30；LiFe0.50Mn0.50PO4Polycrystalline particle be oblate spheroid secondary polycrystalline particle, and polycrystalline The average grain diameter D50 of grain is 7.5 μm, specific surface area BET is 20m2/g；LiFe0.50Mn0.50PO4Polycrystalline particle in LiCoO2's Uniformly continuous is distributed between polycrystalline particle.
Finally illustrate the test process and test result of the lithium rechargeable battery and its positive electrode according to the present invention.
1. the specific surface area BET tests of positive electrode
2g or so powder is scraped from embodiment 1-10 and comparative example 1-3 positive pole diaphragm and loads the sample of known weight Guan Zhong, the sample cell that then will be equipped with powder is put into de-aeration stage and is de-gassed, and removes sample cell after degassing, weighs, and fills Enter in analysis station, the weight for subtracting sky sample cell with the weight of the sample cell equipped with powder after degassing obtains the accurate of powder Weight, as parameter input test software, and starts test, you can measure the specific surface area BET of positive electrode.Wherein, The degassing of powder, the test of the specific surface area of positive electrode and corresponding test result analysis compare surface in NOVA 2000e Carried out on analyzer.
The available gram volume test of 2 positive plates
Weighed after embodiment 1-10 and comparative example 1-3 positive plate are punched into standard button point pole piece, be then assembled into button Formula battery, afterwards at 25 DEG C, with 0.1C (185mA) constant-current charges to 4.4V, afterwards with 4.4V constant-voltage charges to 0.02C (37mA), then with 0.1C (185mA) constant-current discharges to 3.05V, this is charge and discharge cycles process, this is filled for 5 times repeatedly Discharge cycles, take the average value of the discharge capacity of latter 3 times divided by the weight of standard button point pole piece to hold as available gram of positive plate Amount.
3. the high rate performance test of lithium rechargeable battery
At 25 DEG C, with 0.5C (925mA) constant-current charges to 4.35V, afterwards with 4.35V constant-voltage charges to 0.05C (92.5mA), then with 0.5C (925mA) constant-current discharges to 3.0V, obtained discharge capacity is used as lithium rechargeable battery first Discharge capacity after secondary circulation；Again with 0.5C (925mA) constant-current charges to 4.35V, afterwards with 4.35V constant-voltage charges to 0.05C (92.5mA), then with 2C (3700mA) constant-current discharges to 3.0V, obtained discharge capacity is used as lithium rechargeable battery second Discharge capacity after secondary circulation.
Discharge capacity/first time after lithium rechargeable battery 2C/0.5C discharge-rates (%)=second is circulated is circulated Discharge capacity × 100% afterwards.
4. the cycle performance test of lithium rechargeable battery
At 25 DEG C, with 0.5C (925mA) constant-current charges to 4.35V, afterwards with 4.35V constant-voltage charges to 0.05C (92.5mA), then with 0.5C (925mA) constant-current discharges to 3.0V, this is charge and discharge cycles process, repeatedly 1000 times this Plant charge and discharge cycles.
The discharge capacity after the circulation of capability retention (%)=1000th time after the circulation of lithium rechargeable battery 1000 times/ Discharge capacity × 100% after circulating for the first time.
5. the security performance test of lithium rechargeable battery
Every group is randomly selected 5 lithium rechargeable batteries, is completely charged to 4.35V, then carries out standard drift bolt test, the flames of anger Generation is judged to passing through, and burn the percent of pass on fire for being determined as failure, calculating the standard drift bolt test of lithium rechargeable battery.
Table 1 provides embodiment 1-10 and comparative example 1-3 parameter and the performance test results.
The performance test results to embodiment 1-10 and comparative example 1-3 are analyzed below.
As can be seen that the present invention's is less including average grain diameter D50 from the contrast of embodiment 1-10 and comparative example 1 LiFexMn1-xPO4Polycrystalline particle and the larger LiCoO of average grain diameter D502Polycrystalline particle positive electrode, only include relatively LiCoO larger average grain diameter D502Polycrystalline particle positive electrode for, the specific surface area of positive electrode can be effectively improved BET, so as to improve the electrolyte adsorbance of lithium rechargeable battery, and then improve lithium rechargeable battery high rate performance and Cycle performance, while improving the security performance of lithium rechargeable battery.This is due to the LiFe of the present inventionxMn1-xPO4Polycrystalline Grain has higher porosity and specific surface area, has stronger compatibility with electrolyte, is filled with larger in average grain diameter D50 LiCoO2Polycrystalline particle between, the electrolyte adsorbance of positive electrode can be effectively improved, improve lithium rechargeable battery High rate performance, cycle performance while, and do not produce rise liquid deformation etc. infringement, so as to improve the safety of lithium rechargeable battery Performance.While LiFexMn1-xPO4For LiCoO2The expansion produced during Li insertion extraction/contraction provides certain cushion space, LiFe can also be made upxMn1-xPO4Deficiency in terms of compacted density, reduces its influence to maximum system energy density, so as to improve just Structural stability of the pole material in cyclic process.In addition, LiFexMn1-xPO4With higher heat endurance and chemically stable Property, the generation rate of electrolyte in storing process in side reactions such as the oxidation Decompositions of pole piece can be effectively reduced, and then improve The storage performance of lithium rechargeable battery, and greatly improve the security performance of lithium rechargeable battery.
As can be seen that the present invention's is less including average grain diameter D50 from the contrast of embodiment 1-10 and comparative example 2 LiFexMn1-xPO4Polycrystalline particle and the larger LiCoO of average grain diameter D502Polycrystalline particle positive electrode, only include relatively The less LiFe of average grain diameter D50xMn1-xPO4Polycrystalline particle positive electrode for, can make lithium rechargeable battery have compared with Good high rate performance, cycle performance and security performance, while also making positive electrode that there is higher available gram volume.This be by In LiCoO2Average grain diameter D50 it is larger, higher structural stability and heat endurance can be obtained, larger pressure is advantageously implemented Real density, so as to improve the energy density of positive electrode.
As can be seen that fixed LiFe from embodiment 1-5 contrastxMn1-xPO4X be 0.25, LiFexMn1-xPO4With LiCoO2Mass ratio m value increase to 0.45 from 0.05.Work as m<When 0.20, i.e. LiFexMn1-xPO4Content it is relatively low when it is (real Apply a 1-2), although lithium rechargeable battery is tested without 100% by standard drift bolt, compared with comparative example 1, its security It can greatly improve；As 0.20≤m≤0.45, i.e. LiFexMn1-xPO4Content it is higher when (embodiment 3-5), use this hair The lithium rechargeable battery of bright positive electrode 100% can be tested by standard drift bolt.Work as m<When 0.20 (embodiment 1-2), Kept using the capacity after the 2C/0.5C discharge-rates of the lithium rechargeable battery of the positive electrode of the present invention and 1000 circulations Rate is also all relatively low；As 0.20≤m≤0.45 (embodiment 3-5), the lithium rechargeable battery of the positive electrode of the present invention is used 2C/0.5C discharge-rates and 1000 times circulation after capability retention it is all higher.
As can be seen that fixed LiFe from embodiment 6-9 contrastxMn1-xPO4With LiCoO2Mass ratio m be 0.30, LiFexMn1-xPO4Middle x value increases to 0.40 from 0.10, and now lithium rechargeable battery energy 100% is surveyed by standard drift bolt Examination.But in embodiment 6 and embodiment 7, due to LiFexMn1-xPO4Middle x is smaller so that LiFexMn1-xPO4Ionic conductance Rate and electronic conductivity are all relatively low, so that the capacity after the 2C/0.5C discharge-rates of lithium rechargeable battery and 1000 circulations Conservation rate is all relatively low, it is impossible to while obtaining security performance, high rate performance and all preferable lithium rechargeable battery of cycle performance. In embodiment 8-9, due to LiFexMn1-xPO4In x it is larger so that LiFexMn1-xPO4Ionic conductivity and electronic conductance Rate is all higher, so that the capability retention after the 2C/0.5C discharge-rates of lithium rechargeable battery and 1000 circulations is all higher, Therefore all preferable lithium rechargeable battery of security performance, high rate performance and cycle performance can be obtained simultaneously.But work as LiFexMn1-xPO4In x it is excessive when, as shown in comparative example 3, x is 0.50, now LiFexMn1-xPO4Middle voltage platform is 3.2V LiFePO4Content it is excessive, cause LiFexMn1-xPO4High rate performance and the advantage of capability retention gradually reduce, therefore The high rate performance and cycle performance of lithium rechargeable battery are all poor.
As can be seen that the LiFe with porous network structure from the contrast of embodiment 8 and embodiment 10xMn1-xPO4Just Pole material has higher BET, and the available gram volume of positive plate is higher, while the cycle performance of lithium rechargeable battery is also obtained Improve.This is due to LiFexMn1-xPO4Porous network structure can make it have larger available gram volume and higher Working voltage platform, and can be with LiCoO2Match, so as to ensure LiCoO2Advantage in energy density.In addition, can also pass through LiFexMn1-xPO4Higher discharge platform improve the discharge potential of positive electrode, the polarization resistance on reduction positive electrode surface It is anti-, make up LiFexMn1-xPO4Deficiency in energy density, make lithium rechargeable battery have higher energy density and compared with Long cycle life.
The embodiment 1-10 of table 1 and comparative example 1-3 parameter and the performance test results

Claims (15)

1. a kind of positive electrode, it is characterised in that
The positive electrode includes cobalt acid lithium LiCoO2And iron manganese phosphate for lithium LiFexMn1-xPO4, wherein, 0<x≤0.4；
The iron manganese phosphate for lithium LiFexMn1-xPO4With the cobalt acid lithium LiCoO2Mass ratio be m, and 0<m≤0.45；
The iron manganese phosphate for lithium LiFexMn1-xPO4For the polycrystalline particle with olivine structural；
The cobalt acid lithium LiCoO2For the polycrystalline particle with layer structure；
The iron manganese phosphate for lithium LiFexMn1-xPO4Polycrystalline particle average grain diameter D50 be less than the cobalt acid lithium LiCoO2It is many The average grain diameter D50 of brilliant particle, and the iron manganese phosphate for lithium LiFexMn1-xPO4Polycrystalline particle be filled in the cobalt acid lithium LiCoO2Polycrystalline particle between.
2. positive electrode according to claim 1, it is characterised in that 0.25≤x≤0.4.
3. positive electrode according to claim 1, it is characterised in that the iron manganese phosphate for lithium LiFexMn1-xPO4Polycrystalline Particle is secondary polycrystalline particle.
4. positive electrode according to claim 3, it is characterised in that the secondary polycrystalline particle is oblate spheroid, elliposoidal Or it is spherical.
5. positive electrode according to claim 3, it is characterised in that the secondary polycrystalline particle has holey knot Structure.
6. positive electrode according to claim 3, it is characterised in that
The average grain diameter D50 of the secondary polycrystalline particle is 2.5 μm~15 μm；
The specific surface area BET of the secondary polycrystalline particle is 10m2/ g~30m2/g。
7. positive electrode according to claim 6, it is characterised in that
The average grain diameter D50 of the secondary polycrystalline particle is 2.5 μm~15 μm；
The specific surface area BET of the secondary polycrystalline particle is 20m2/g。
8. positive electrode according to claim 6, it is characterised in that
The average grain diameter D50 of the secondary polycrystalline particle is 7 μm~8 μm；
The specific surface area BET of the secondary polycrystalline particle is 10m2/ g~30m2/g。
9. positive electrode according to claim 6, it is characterised in that
The average grain diameter D50 of the secondary polycrystalline particle is 7 μm~8 μm；
The specific surface area BET of the secondary polycrystalline particle is 20m2/g。
10. positive electrode according to claim 1, it is characterised in that the cobalt acid lithium LiCoO2Polycrystalline particle be averaged Particle diameter D50 is 5 μm~20 μm.
11. positive electrode according to claim 10, it is characterised in that the cobalt acid lithium LiCoO2Polycrystalline particle it is flat Equal particle diameter D50 is 9 μm~10 μm.
12. positive electrode according to claim 1, it is characterised in that the cobalt acid lithium LiCoO2Polycrystalline particle ratio table Area B ET is 0.1m2/ g~0.6m2/g。
13. positive electrode according to claim 12, it is characterised in that the cobalt acid lithium LiCoO2Polycrystalline particle ratio Surface area BET is 0.5m2/g。
14. positive electrode according to claim 1, it is characterised in that the iron manganese phosphate for lithium LiFexMn1-xPO4Polycrystalline Particle is in the cobalt acid lithium LiCoO2Polycrystalline particle between distribution mode be distributed for uniformly continuous or uniform discontinuously arranged.
15. a kind of lithium rechargeable battery, including：
Negative plate, including negative current collector, be arranged on negative current collector and the cathode membrane comprising negative material；
Positive plate, including plus plate current-collecting body, be arranged on plus plate current-collecting body and the positive pole diaphragm comprising positive electrode；
Barrier film, is interval between negative plate and positive plate；And
Electrolyte；
Characterized in that,
The positive electrode is according to any described positive electrode in claim 1-14.
CN201410233927.XA 2014-05-29 2014-05-29 Positive electrode and lithium rechargeable battery Active CN105185987B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201410233927.XA CN105185987B (en) 2014-05-29 2014-05-29 Positive electrode and lithium rechargeable battery
US14/723,273 US20150349330A1 (en) 2014-05-29 2015-05-27 Positive active material and lithium-ion secondary battery
US16/115,395 US20180366720A1 (en) 2014-05-29 2018-08-28 Positive active material and lithium-ion secondary battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410233927.XA CN105185987B (en) 2014-05-29 2014-05-29 Positive electrode and lithium rechargeable battery

Publications (2)

Publication Number Publication Date
CN105185987A CN105185987A (en) 2015-12-23
CN105185987B true CN105185987B (en) 2017-09-12

Family

ID=54702827

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410233927.XA Active CN105185987B (en) 2014-05-29 2014-05-29 Positive electrode and lithium rechargeable battery

Country Status (2)

Country Link
US (2) US20150349330A1 (en)
CN (1) CN105185987B (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106207114A (en) * 2016-07-19 2016-12-07 青岛富强新材料科技有限公司 A kind of preparation method of low ferrum lithium porous LiFePO4 positive electrode
CN107359342B (en) * 2017-07-27 2019-12-24 泓辰电池材料有限公司 Lithium ferromanganese phosphate particles and lithium ferromanganese phosphate powder
CN107665983B (en) * 2017-08-07 2021-01-12 深圳市德方纳米科技股份有限公司 Lithium ion battery positive electrode material, preparation method thereof and lithium ion battery
KR102553570B1 (en) * 2018-06-27 2023-07-10 삼성전자 주식회사 Cathode active material for lithium ion battery and lithium ion battery comprising the same
CN109742339B (en) * 2018-12-14 2023-05-02 江苏海四达电源有限公司 High-specific-energy ultralow-temperature high-safety polymer lithium ion battery and preparation method thereof
CN109962221B (en) * 2019-02-20 2020-03-17 江西星盈科技有限公司 Composite positive electrode material, positive plate, preparation method of positive plate and lithium ion battery
CN112864360A (en) * 2019-11-28 2021-05-28 珠海冠宇电池股份有限公司 High-voltage positive pole piece and lithium ion secondary battery containing same
JP6841362B1 (en) * 2020-03-17 2021-03-10 住友大阪セメント株式会社 Positive electrode material for lithium ion secondary batteries, positive electrode for lithium ion secondary batteries and lithium ion secondary batteries
EP4075538A4 (en) * 2020-08-31 2023-01-25 Contemporary Amperex Technology Co., Limited Secondary battery and preparation method therefor, and battery module, battery pack and device comprising secondary battery
CN112133900A (en) * 2020-09-27 2020-12-25 上海华谊（集团）公司 Positive electrode active material and lithium ion battery containing the same
CN115863620A (en) * 2021-09-24 2023-03-28 比亚迪股份有限公司 Battery anode material and application thereof
CN114023952B (en) * 2021-11-02 2023-02-24 珠海冠宇电池股份有限公司 Positive active material, positive plate and lithium ion battery
CN115799441B (en) * 2023-02-10 2023-07-14 欣旺达电动汽车电池有限公司 Lithium ion battery and power utilization device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1320976A (en) * 2000-04-25 2001-11-07 索尼株式会社 Positive electrode and non-aqueous electrolyte cell
CN1349273A (en) * 2000-10-05 2002-05-15 索尼株式会社 Solid electrolyte cell
CN101388459A (en) * 2007-09-11 2009-03-18 深圳市比克电池有限公司 Preparation of ferric phosphate composite positive pole
WO2013016426A1 (en) * 2011-07-25 2013-01-31 A123 Systems, Inc. Blended cathode materials
EP2562857A2 (en) * 2010-04-21 2013-02-27 LG Chem, Ltd. Lithium iron phosphate with carbon-coated olivine crystal structure and lithium secondary battery using the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102300706B1 (en) * 2013-09-20 2021-09-09 바스프 에스이 Electrode materials for lithium ion batteries

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1320976A (en) * 2000-04-25 2001-11-07 索尼株式会社 Positive electrode and non-aqueous electrolyte cell
CN1349273A (en) * 2000-10-05 2002-05-15 索尼株式会社 Solid electrolyte cell
CN101388459A (en) * 2007-09-11 2009-03-18 深圳市比克电池有限公司 Preparation of ferric phosphate composite positive pole
EP2562857A2 (en) * 2010-04-21 2013-02-27 LG Chem, Ltd. Lithium iron phosphate with carbon-coated olivine crystal structure and lithium secondary battery using the same
WO2013016426A1 (en) * 2011-07-25 2013-01-31 A123 Systems, Inc. Blended cathode materials

Also Published As

Publication number Publication date
US20180366720A1 (en) 2018-12-20
US20150349330A1 (en) 2015-12-03
CN105185987A (en) 2015-12-23

Similar Documents

Publication Publication Date Title
CN105185987B (en) Positive electrode and lithium rechargeable battery
CN105552344B (en) A kind of based lithium-ion battery positive plate, lithium ion battery and preparation method thereof
CN103700820B (en) A kind of lithium ion selenium battery with long service life
CN106058222B (en) Polymer carbonization in-situ coated ferric trifluoride composite cathode material and preparation method thereof
CN103996820A (en) Lithium ion battery as well as mixed positive electrode and active material with synergistic effect
CN107154486A (en) A kind of cupric multi-element metal sulfide is the sodium-ion battery of negative material
CN109950538A (en) A kind of vanadium base anode material of Zinc ion battery
CN105692576A (en) Method for preparing battery-grade FePO4 from industrial iron-containing waste
CN109659511B (en) SiO (silicon dioxide)2Coated ternary positive electrode material and preparation method thereof
CN104795564B (en) A kind of positive electrode of Aqueous solution secondary battery, pole piece, secondary cell and purposes
CN110098387B (en) Lithium phosphate and conductive carbon material coated ternary cathode material and preparation method and application thereof
CN105226267B (en) Three dimensional carbon nanotubes modification spinel nickel lithium manganate material and its preparation method and application
CN106410194A (en) Composite lithium battery and preparation method thereof
CN101222038A (en) Production method of lithium ion power cell ferrous phosphate lithium composite material
CN105591100A (en) Method of preparing lithium iron phosphate cathode material through hydrothermal method, and the cathode material
CN101262056A (en) A water solution chargeable lithium ion battery
CN106972162A (en) A kind of sodium-ion battery double-doped hard carbon microballoon of negative material phosphorus sulphur and preparation method thereof
CN102263280A (en) Flow aqueous chargeable alkali metal ion battery
CN114188508B (en) Lithium iron phosphate cathode material, preparation method and application
CN101483237A (en) Preparation of positive pole material lithium ionic phosphate of long cycle life electrokinetic cell
CN104810513A (en) Lithium ion battery cathode material and preparation method thereof
CN107706393B (en) High-capacity solid lithium ion battery and preparation method thereof
CN102769134B (en) Preparation method of lithium ion battery anode composite material LiFePO4/C
CN111916703A (en) In-situ synthesis method of lithium iron manganese phosphate/carbon @ graphene composite material
CN107104224A (en) A kind of lithium iron phosphate positive material preparation method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant